Yttrium oxide based coating composition

ABSTRACT

Described herein is a protective coating composition that provides erosion and corrosion resistance to a coated article (such as a chamber component) upon the article&#39;s exposure to harsh chemical environment (such as hydrogen based and/or halogen based environment) and/or upon the article&#39;s exposure to high energy plasma. Also described herein is a method of coating an article with the protective coating using electronic beam ion assisted deposition, physical vapor deposition, or plasma spray. Also described herein is a method of processing wafer, which method exhibits, on average, less than about 5 yttrium based particle defects per wafer.

TECHNICAL FIELD

Embodiments of the present invention relate, in general, to a method ofcoating chamber components with a yttrium oxide based protective coatingcomposition using ion assisted deposition, plasma spray, or physicalvapor deposition.

BACKGROUND

In the semiconductor industry, devices are fabricated by a number ofmanufacturing processes producing structures of an ever-decreasing size.As device geometries shrink, controlling the process uniformity andrepeatability become much more challenging.

Existing manufacturing processes expose semiconductor processing chambercomponents to high energy aggressive plasma and/or corrosive environmentwhich may be harmful to the integrity of the semiconductor processingchamber components and may further contribute to the challenge ofcontrolling process uniformity and repeatability.

Hence, certain semiconductor processing chamber components (e.g.,liners, doors, lids, and so on) are coated with yttrium based protectivecoatings. Yttria (Y₂O₃) is commonly used in etch chamber components dueto its good erosion and/or sputtering resistance in aggressive plasmaenvironment.

It would be advantageous to arrive at a protective coating that providesboth physical resistance to sputtering occurring from high energyaggressive plasma and chemical resistance to corrosion occurring fromcorrosive environments.

BRIEF SUMMARY OF EMBODIMENTS

In certain embodiments, the instant disclosure is directed to a coatedchamber component. The coated chamber component includes a body and acorrosion and erosion resistant coating. The corrosion and erosionresistant coating includes a single phase blend of yttrium oxide at amolar concentration ranging from about 0.1 mole % up to 37 mole % andaluminum oxide at a molar concentration ranging from above 63 mole % toabout 99.9 mole %.

In certain embodiments, the instant disclosure is directed to a methodfor coating a chamber component. The method includes performing electronbeam ion assisted deposition (e-beam IAD), physical vapor deposition(PVD), or plasma spray to deposit a corrosion and erosion resistantcoating. The corrosion and erosion resistant coating includes a singlephase blend of yttrium oxide at a molar concentration ranging from about0.1 mole % up to 37 mole % and aluminum oxide at a molar concentrationranging from above 63 mole % to about 99.9 mole %.

In certain embodiments, the instant disclosure is directed to a methodfor processing a wafer. The method includes processing a wafer in achamber that includes at least one chamber component coated with acorrosion and erosion resistant coating. The corrosion and erosionresistant coating includes a single phase blend of yttrium oxide at amolar concentration ranging from about 0.1 mole % up to 37 mole % andaluminum oxide at a molar concentration ranging from above 63 mole % toabout 99.9 mole %.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is illustrated by way of example, and not by wayof limitation, in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that differentreferences to “an” or “one” embodiment in this disclosure are notnecessarily to the same embodiment, and such references mean at leastone.

FIG. 1 depicts a sectional view of one embodiment of a processingchamber.

FIG. 2A depicts a deposition mechanism applicable to a variety ofdeposition techniques utilizing energetic particles such as ion assisteddeposition (IAD).

FIG. 2B depicts a schematic of an IAD deposition apparatus.

FIG. 3 illustrates cross sectional side views of articles (e.g., lids)covered by one or more protective coatings.

FIG. 4A illustrates a perspective view of a chamber lid having aprotective coating, in accordance with one embodiment.

FIG. 4B illustrates a cross-sectional side view of a chamber lid havinga protective coating, in accordance with one embodiment.

FIG. 5 illustrates a method for coating an article with a protectivecoating according to an embodiment.

FIG. 6 illustrates a method for processing a wafer in a processingchamber that includes at least one chamber component coated with aprotective coating according to an embodiment.

FIG. 7 illustrates a phase diagram of alumina and yttria.

FIG. 8 shows total yttrium-based particles during a 700 RFhrs chambermarathon running aggressive chemistry using a protective coatingaccording to an embodiment as compared to a comparative YO coating.

FIG. 9 shows the total yttrium-based defects per wafer of a protectivecoating according to an embodiment as compared to a comparative YOcoating.

FIGS. 10A, 10B, 10C, and 10D show the chemical resistance of aprotective coating according to an embodiment (FIG. 10D) as compared toa comparative YO coating (FIG. 10A), a comparative YAM coating (FIG.10B), and a comparative YAG coating (FIG. 10C) upon the coatings'exposure to an acid stress test.

FIG. 11 depicts a schematic of a physical vapor deposition techniquethat may be utilized to deposit a protective coating according to anembodiment.

FIG. 12 depicts a schematic of a plasma spray deposition technique thatmay be utilized to deposit a protective coating according to anembodiment.

DETAILED DESCRIPTION OF EMBODIMENTS

Semiconductor manufacturing processes expose semiconductor processchamber components to high energy aggressive plasma environments and tocorrosive environments. To protect the process chamber components fromthese aggressive environments, chamber components are coated withprotective coatings.

Yttria (Y₂O₃) is commonly used in coatings of chamber components (e.g.,etch chamber components) for its good erosion resistance. Despite itsgood erosion resistance, yttria is not chemically stable in aggressiveetch chemistries. Radicals like Fluorine, Chlorine and Bromide easilyattack yttria chemically, contributing to the formation of yttrium-basedparticles. yttrium-based particles contribute to defects in etchapplications. Hence, various industries (e.g., logic industry) havebegun to set tight specifications for yttrium-based defects on productwafers.

To meet these tight specifications, it is beneficial to identifyprotective coating compositions that provide both physical resistance tosputtering occurring due to high energy aggressive plasma and chemicalresistance occurring due to chemical attacks by aggressive chemicalenvironments.

In this disclosure a protective coating has been identified havingimproved chemical stability compared to pure yttria (Y₂O₃) and otheryttrium-based materials while also maintaining physical resistance tohigh energy aggressive plasma compared to pure alumina (Al₂O₃).

In certain embodiments, the protective coating described herein is acorrosion and erosion resistant coating that includes a single phaseblend of aluminum oxide and yttrium oxide. In certain embodiments, theprotective coating is amorphous. Due to the amorphous nature of theprotective coating, it may include more alumina than could otherwise beincluded in a coating that is in a crystalline phase. A crystallinecoating of yttria and alumina is constrained to the phases depicted inthe alumina-yttria phase diagram, such as the one shown in FIG. 7 . Forinstance, according to region A in the phase diagram of FIG. 7 ,spanning from a yttria mole fraction greater than 0 but less than about0.37 (the yttria mole fraction associated with the first vertical line Bin the phase diagram which is representative of the crystalline phaseyttrium aluminum garnet (YAG)), at a temperature below about 2080 K, acrystalline yttria-alumina coating with two phases would form, namely—acrystalline YAG phase and a crystalline alumina phase. Coatingsdescribed herein deviate from the conventional phase diagram by forminga single phase (e.g., amorphous phase) of alumina and yttria blend witha composition of alumina and yttria that would otherwise fall in the Aregion.

Without being construed as limiting, it is believed that due to theamorphous nature of certain coatings described herein, it is possible tointroduce more of the aluminum-based component into the coating andrender the coating more chemically resistant to harsh chemicalenvironments (e.g., acidic environments, hydrogen based environments,and halogen based environments) while still maintaining a sufficientamount of the yttrium-based component in the coating to render itphysically resistant to high energy plasma environments.

In certain embodiments, the instant disclosure is directed to a methodfor coating a chamber component with any of the protective coatingsdescribed herein. Any chamber component that is exposed to the harshchemical environments and/or to the high energy plasma environments in aprocessing chamber may be coated with the protective coatings describedherein. The chamber components may be coated on the processingenvironment facing side and optionally on other sides. Suitable chambercomponents that could benefit from such coatings include, withoutlimitation, lids, liners, doors, nozzles, and so on. The protectivecoating may be formed on the processing environment (e.g., plasmaenvironment and/or chemical environment) facing side of the body of thechamber component using ion assisted deposition (IAD) (e.g., usingelectron beam IAD (EB-IAD)). In certain embodiments, the protectivecoating may be formed using plasma spray deposition or physical vapordeposition. The improved corrosion and/or erosion resistance provided bythe protective coating may improve the service life of the coatedarticle, while reducing maintenance and manufacturing cost.Additionally, the coating described herein (whether deposited via IAD,PVD, or plasma spray) can be applied thick enough to provide a longerlife time for the component as compared to other yttrium based coatings(deposited by a similar deposition technique) or as compared to anuncoated component.

In certain embodiments, the instant disclosure is further directed to amethod for processing a wafer in a processing chamber that includes atleast one chamber component coated with the protective coatingsdescribed herein. Due to the improved corrosion and/or erosionresistance provided by the protective coating, the coated chambercomponents produce less yttrium based particles, which have become amajor contributor to wafer defects. Tight specifications are set aroundyttrium-based particles and corresponding yttrium-based defects with theultimate goal of eliminating yttrium-based defects in wafers altogether.Wafers processed in processing chambers with at least one chambercomponent coated with the protective coatings described herein exhibit,on average, less than about 1 yttrium-based particle defect per wafer.In comparison, wafers processed in processing chambers where the chambercomponents are coated with comparative protective coatings exhibit, onaverage, more than about 8 yttrium-based particle defects per wafer.

FIG. 1 is a sectional view of a semiconductor processing chamber 100having one or more chamber components that are coated with a protectivecoating in accordance with embodiments of the present disclosure. Theprocessing chamber 100 may be used for processes in which aggressiveplasma environment and/or aggressive chemical environment is provided.For example, the processing chamber 100 may be a chamber for a plasmaetch reactor (also known as a plasma etcher), a plasma cleaner, and soforth. Examples of chamber components that may include a protectivecoating include a substrate support assembly 148, an electrostatic chuck(ESC) 150, a ring (e.g., a process kit ring or single ring), a chamberwall, a base, a gas distribution plate, a showerhead, a liner, a linerkit, a shield, a plasma screen, a flow equalizer, a cooling base, achamber viewport, a chamber lid 130, a nozzle, and so on. In oneparticular embodiment, the protective coating is applied over a chamberlid 130 and/or a liner 116.

In certain embodiments, the protective coating, which is described ingreater detail below, is a single phase amorphous coating that is ablend of yttrium oxide at a molar concentration of about 0.1 mole % toup to 37 mole % and aluminum oxide at a molar concentration of above 63mole % to about 99.9 mole % deposited by electron beam ion assisteddeposition (e-beam IAD). Alternatively, other forms of IAD may be usedto deposit the coating. Alternatively, other deposition techniques suchas physical vapor deposition (PVD) or plasma spray may be used todeposit the coating.

In certain embodiments, the protective coating includes yttrium oxide ata molar concentration of about 10 mole % to up to 37 mole % and aluminumoxide at a molar concentration of above 63 mole % to about 90 mole %. Incertain embodiments, the protective coating includes yttrium oxide at amolar concentration of about 15 mole % to up to 37 mole % and aluminumoxide at a molar concentration of above 63 mole % to about 85 mole %. Incertain embodiments, the protective coating includes yttrium oxide at amolar concentration of about 5 mole % to about 35 mole % and aluminumoxide at a molar concentration of about 65 mole % to about 95 mole %. Incertain embodiments, the protective coating includes yttrium oxide at amolar concentration of about 5 mole % to about 30 mole % and aluminumoxide at a molar concentration of about 70 mole % to about 95 mole %. Incertain embodiments, the protective coating includes yttrium oxide at amolar concentration of about 5 mole % to about 20 mole % and aluminumoxide at a molar concentration of about 80 mole % to about 95 mole %. Incertain embodiments, the molar concentration of yttrium oxide andaluminum oxide in the protective coating adds up to 100 mole %.

In certain embodiments, the protective coating includes yttrium oxide ata molar concentration ranging from any of about 0.1 mole %, about 0.5mole %, about 1.0 mole %, about 2 mole %, about 3 mole %, about 4 mole%, about 5 mole %, about 6 mole %, about 7 mole %, about 8 mole %, about9 mole %, about 10 mole %, about 11 mole %, about 12 mole %, about 13mole %, about 14 mole %, about 15 moles %, about 16 mole %, about 17mole %, about 18 mole %, about 19 mole %, or about 20 mole % to any ofabout 21 mole %, about 22 mole %, about 23 mole %, about 24 mole %,about 25 mole %, about 26 mole %, about 27 mole %, about 28 mole %,about 29 mole %, about 30 mole %, about 31 mole %, about 32 mole %,about 33 mole %, about 34 mole %, about 35 mole %, about 36 mole %, orup to 37 mole %, any single value therein or any sub-range therein.

In certain embodiments, the protective coating includes aluminum oxideat a molar concentration ranging from any of above 63 mole %, about 64mole %, about 65 mole %, about 66 mole %, about 67 mole %, about 68 mole%, about 69 mole %, about 70 mole %, about 71 mole %, about 72 mole %,about 73 mole %, about 74 mole %, about 75 mole %, about 76 mole %,about 77 mole %, about 78 mole %, about 79 mole %, or about 80 mole % toany of about 81 mole %, about 82 mole %, about 83 mole %, about 84 mole%, about 85 mole %, about 86 mole %, about 87 mole %, about 88 mole %,about 89 mole %, about 90 mole %, about 91 mole %, about 92 mole %,about 93 mole %, about 94 mole %, about 95 mole %, about 96 mole %,about 97 mole %, about 98 mole %, about 99 mole %, about 99.5 mole %, orabout 99.9 mole %, or any single value therein or any sub-range therein.

In certain embodiments, the protective coating described herein consistsof or consists essentially of a single phase amorphous blend of aluminumoxide and yttrium oxide, wherein the aluminum oxide is present in theprotective coating at a molar concentration ranging from above 63 mole %to about 99.9 mole %, from above 63 mole % to about 90 mole %, fromabove 63 mole % to about 85 mole %, from about 65 mole % to about 95mole %, from about 70 mole % to about 95 mole %, or from about 80 mole %to about 95 mole % and the yttrium oxide is present in the protectivecoating at a molar ranging from about 0.1 mole % to up to 37 mole %,from about 10 mole % to up to 37 mole %, from about 15 mole % to up to37 mole %, from about 5 mole % to about 35 mole %, from about 5 mole %to about 30 mole %, or from about 5 mole % to about 20 mole %.

The protective coatings described herein provide the flexibility ofincorporating a greater amount of aluminum oxide, which provides for agreater chemical stability to harsh chemical environments (such asacidic environment, hydrogen based environments, and halogen basedenvironments) as compared to other yttrium based coatings or yttrium andaluminum based coatings that are constrained to the alumina-yttria phasediagram depicted in FIG. 7 . It is possible to incorporate more aluminainto protective coatings described herein due to their amorphous naturein which bond links can and do vary (as compared to bond links in phasesthat are constrained to the alumina-yttria phase diagram of FIG. 7 ).

FIG. 7 depicts a phase diagram of yttria and alumina at varioustemperatures. In region A, ranging from above 0 mole % yttria to below37 mole % yttria and from above 63 mole % alumina to below 100 mole %alumina, at a temperature below about 2080 K (e.g., below 2084 K), thephase diagram exhibits a two phase system crystalline alumina andcrystalline YAG (yttrium aluminum garnet). In the midway of region A, ata temperature below about 2080 K (e.g., below 2084 K), the two phases,YAG and alumina, are present at approximately equal amounts (i.e., about1:1 mole alumina to mole YAG). To the left of the midway of region A(i.e., closer to pure alumina), at a temperature below about 2080 K(e.g., below 2084 K), crystalline alumina is the majority phase andcrystalline YAG is the minority phase. To the right of the midway ofregion A, at a temperature below about 2080 K (e.g., below 2084 K),crystalline YAG is the majority phase and crystalline alumina is theminority phase. At the first vertical line, designated as B(corresponding to the temperature of 2197 K), in the phase diagram, atabout 37 mole % yttria and about 63 mole % alumina, crystalline YAGforms. It is believed, without being construed as limiting, thatstarting from any point in the phase diagram, on the crystalline YAGline or in the dual phase region of crystalline alumina and crystallineYAG, at a temperature below 2084 K, and attempting to add more aluminato the composition, would provide a two distinct phase system ofcrystalline alumina and crystalline YAG (e.g., alumina particles may bedispersed in a YAG matrix). However, such composition would provide lesschemical resistance than the amorphous coating described herein.

In certain embodiments, the protective coatings described herein have acoating composition that includes aluminum at a concentration rangingfrom any of about 20 atom %, about 21 atom %, about 22 atom %, about 23atom %, about 24 atom %, about 25 atom %, about 26 atom %, about 27 atom%, about 28 atom %, about 29 atom %, or about 30 atom % to any of about31 atom %, about 32 atom %, about 33 atom %, about 34 atom %, about 35atom %, about 36 atom %, about 37 atom %, about 38 atom %, about 39 atom%, about 40 atom %, about 41 atom %, about 42 atom %, about 43 atom %,about 44 atom %, or about 45 atom %, or any single value therein or anysub-range therein. In one embodiment, the aluminum concentration in theprotective coating ranges from about 20 atom % to about 35 atom %. Inone embodiment, the aluminum concentration in the protective coatingranges from about 27 atom % to about 44 atom %.

In certain embodiments, the protective coatings described herein have acoating composition that includes yttrium at a concentration rangingfrom any of about 1 atom %, about 2 atom %, about 3 atom %, about 4 atom%, about 5 atom %, about 6 atom %, about 7 atom %, about 8 atom %, about9 atom %, or about 10 atom % to any of about 11 atom %, about 12 atom %,about 13 atom %, about 14 atom %, about 15 atom %, about 16 atom %,about 17 atom %, about 18 atom %, about 19 atom %, or about 20 atom %,or any single value therein or any sub-range therein. In one embodiment,the yttrium concentration in the protective coating ranges from about 1atom % to about 8 atom %. In one embodiment, the yttrium concentrationin the protective coating ranges from about 8 atom % to about 18 atom %.

In certain embodiments, the protective coatings described herein have acoating composition that includes oxygen at a concentration ranging fromany of about 55 atom %, about 56 atom %, about 57 atom %, about 58 atom%, about 59 atom %, about 60 atom %, about 61 atom %, about 62 atom %,or about 63 atom % to any of about 64 atom %, about 65 atom %, about 66atom %, about 67 atom %, about 68 atom %, about 69 atom %, or about 70atom %, or any single value therein or any sub-range therein. In oneembodiment, the oxygen concentration in the protective coating rangesfrom about 55 atom % to about 70 atom %. In one embodiment, the oxygenconcentration in the protective coating ranges from about 62 atom % toabout 70 atom %.

In one embodiment, the protective coating comprises, consists, orconsists essentially of about 27 atom % to about 44 atom % aluminum,about 1 atom % to about 8 atom % yttrium, and about 55 atom % to about70 atom % oxygen. In one embodiment, the protective coating comprises,consists, or consists essentially of about 20 atom % to about 35 atom %aluminum, about 8 atom % to about 18 atom % yttrium, and about 62 atom %to about 70 atom % oxygen.

The ratio of aluminum atom % to yttrium atom % in the protective coatingdescribed herein may range from any of about 1, about 1.5, about 2,about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 6,about 7, about 8, about 9, or about 10 to any of about 12, about 14,about 16, about 18, about 20, about 22, about 24, about 26, about 28,about 30, about 34, about 38, about 42, or about 44. In one embodiment,the ratio of aluminum atom % to yttrium atom % in the protective coatingranges from about 1 to about 4.5. In one embodiment, the ratio ofaluminum atom % to yttrium atom % ranges from about 3.4 to about 44.

The protective coating composition is determined by Scanning ElectronMicroscope Energy Dispersive Spectroscopy (SEM-EDS) analysis with amagnification of 1000x and accelerating voltage of 10 keV.

In certain embodiments, the coating described herein provides a greaterchemical resistance as compared to YAG or as compared to multi-phasecompositions including YAG in combination with other material (such asalumina). In certain embodiments, the coating described herein includesa single phase amorphous blend of yttria and alumina, which includes agreater concentration of alumina/aluminum as compared to the amount ofalumina/aluminum in YAG.

In certain embodiments, the protective coating described herein has nocrystalline areas therein. In certain embodiments, the protectivecoating has no free alumina, no free yttria, and/or no YAG therein. Incertain embodiments, the protective coating is more than about 90%amorphous, more than about 92% amorphous, more than about 94% amorphous,more than about 96% amorphous, more than about 98% amorphous, or morethan about 99% amorphous as measured by X-Ray Diffraction (XRD).

The protective coating may be an e-beam IAD deposited coating, a PVDdeposited coating, or a plasma spray deposited coating applied overdifferent ceramics including oxide based ceramics, nitride basedceramics and/or carbide based ceramics. Examples of oxide based ceramicsinclude SiO₂ (quartz), Al₂O₃, Y₂O₃, and so on. Examples of carbide basedceramics include SiC, Si—SiC, and so on. Examples of nitride basedceramics include AN, SiN, and so on. E-beam IAD coating plug materialcan be calcined powders, preformed lumps (e.g., formed by green bodypressing, hot pressing, and so on), a sintered body (e.g., having50-100% density), or a machined body (e.g., can be ceramic, metal, or ametal alloy). Returning to FIG. 1 , as illustrated, the lid 130, nozzle132, and liner 116 each have a protective coating 133, 134, and 136,respectively, in accordance with one embodiment. However, it should beunderstood that any of the other chamber components, such as thoselisted above, may also include a protective coating.

In one embodiment, the processing chamber 100 includes a chamber body102 and a lid 130 that enclose an interior volume 106. The chamber body102 may be fabricated from aluminum, stainless steel or other suitablematerial. The chamber body 102 generally includes sidewalls 108 and abottom 110. Any of the lid 130, sidewalls 108 and/or bottom 110 mayinclude a protective coating.

An outer liner 116 may be disposed adjacent the sidewalls 108 to protectthe chamber body 102. The outer liner 116 may be fabricated and/orcoated with a protective coating. In one embodiment, the outer liner 116is fabricated from aluminum oxide.

An exhaust port 126 may be defined in the chamber body 102, and maycouple the interior volume 106 to a pump system 128. The pump system 128may include one or more pumps and throttle valves utilized to evacuateand regulate the pressure of the interior volume 106 of the processingchamber 100.

The lid 130 may be supported on the sidewall 108 of the chamber body102. The lid 130 may be opened to allow access to the interior volume106 of the processing chamber 100, and may provide a seal for theprocessing chamber 100 while closed. A gas panel 158 may be coupled tothe processing chamber 100 to provide process and/or cleaning gases tothe interior volume 106 through the nozzle 132. The lid 130 may be aceramic such as Al₂O₃, Y₂O₃, YAG, SiO₂, AlN, SiN, SiC, Si—SiC, or aceramic compound comprising Y₄Al₂O₉ and a solid-solution of Y₂O₃—ZrO₂.The nozzle 132 may also be a ceramic, such as any of those ceramicsmentioned for the lid. The lid 130 and/or nozzle 132 may be coated witha protective coating 133, 134, respectively.

Examples of processing gases that may be used to process substrates inthe processing chamber 100 include halogen-containing gases andhydrogen-containing gases, such as C₂F₆, SF₆, SiCl₄, HBr, NF₃, CF₄,CRF₃, CH₂F₃, F, NF₃, Cl₂, CCl₄, BCl₃, SiF₄, H₂, Cl₂, HCl, HE, amongothers, and other gases such as O₂, or N₂O. Examples of carrier gasesinclude N₂, He, Ar, and other gases inert to process gases (e.g.,non-reactive gases). A substrate support assembly 148 is disposed in theinterior volume 106 of the processing chamber 100 below the lid 130. Thesubstrate support assembly 148 holds the substrate 144 duringprocessing. A ring 146 (e.g., a single ring) may cover a portion of theelectrostatic chuck 150, and may protect the covered portion fromexposure to plasma during processing. The ring 146 may be silicon orquartz in one embodiment.

An inner liner 118 may be coated on the periphery of the substratesupport assembly 148. The inner liner 118 may be a halogen-containinggas resist material such as those discussed with reference to the outerliner 116. In one embodiment, the inner liner 118 may be fabricated fromthe same materials of the outer liner 116. Additionally, the inner liner118 may be coated with a protective coating.

In one embodiment, the substrate support assembly 148 includes amounting plate 162 supporting a pedestal 152, and an electrostatic chuck150. The electrostatic chuck 150 further includes a thermally conductivebase 164 and an electrostatic puck 166 bonded to the thermallyconductive base by a bond 138, which may be a silicone bond in oneembodiment. The mounting plate 162 is coupled to the bottom 110 of thechamber body 102 and includes passages for routing utilities (e.g.,fluids, power lines, sensor leads, etc.) to the thermally conductivebase 164 and the electrostatic puck 166.

The thermally conductive base 164 and/or electrostatic puck 166 mayinclude one or more optional embedded heating elements 176, embeddedthermal isolators 174 and/or conduits 168, 170 to control a lateraltemperature profile of the support assembly 148. The conduits 168, 170may be fluidly coupled to a fluid source 172 that circulates atemperature regulating fluid through the conduits 168, 170. The embeddedisolator 174 may be disposed between the conduits 168, 170 in oneembodiment. The heater 176 is regulated by a heater power source 178.The conduits 168, 170 and heater 176 may be utilized to control thetemperature of the thermally conductive base 164, thereby heating and/orcooling the electrostatic puck 166 and a substrate (e.g., a wafer) 144being processed. The temperature of the electrostatic puck 166 and thethermally conductive base 164 may be monitored using a plurality oftemperature sensors 190, 192, which may be monitored using a controller195.

The electrostatic puck 166 may further include multiple gas passagessuch as grooves, mesas and other surface features, that may be formed inan upper surface of the puck 166. The gas passages may be fluidlycoupled to a source of a heat transfer (or backside) gas such as He viaholes drilled in the puck 166. In operation, the backside gas may beprovided at controlled pressure into the gas passages to enhance theheat transfer between the electrostatic puck 166 and the substrate 144.

The electrostatic puck 166 includes at least one clamping electrode 180controlled by a chucking power source 182. The electrode 180 (or otherelectrode disposed in the puck 166 or base 164) may further be coupledto one or more RF power sources 184, 186 through a matching circuit 188for maintaining a plasma formed from process and/or other gases withinthe processing chamber 100. The sources 184, 186 are generally capableof producing RF signal having a frequency from about 50 kHz to about 3GHz and a power of up to about 10,000 Watts.

FIG. 2A depicts a deposition mechanism applicable to a variety ofdeposition techniques utilizing energetic particles such as ion assisteddeposition (IAD). Exemplary IAD methods include deposition processeswhich incorporate ion bombardment, such as evaporation (e.g., activatedreactive evaporation (ARE)) and sputtering in the presence of ionbombardment to form protective coatings as described herein. Oneparticular type of IAD performed in embodiments is electron beam IAD(e-beam IAD). Any of the IAD methods may be performed in the presence ofa reactive gas species, such as O₂, N₂, halogens (e.g., fluorine), Argonetc. Such reactive species may burn off surface organic contaminantsprior to and/or during deposition. Additionally, the IAD depositionprocess for ceramic target deposition vs. the metal target depositioncan be controlled by partial pressure of 02 ions in embodiments.Alternatively, a ceramic target can be used with no oxygen or reducedoxygen. In certain embodiments, the IAD deposition is performed in thepresence of oxygen and/or argon. In certain embodiments, the IADdeposition is performed in the presence of fluorine so as to deposit thecoating with fluorine incorporated into the coating. Coatings withfluorine incorporated therein are believed to be less likely to interactwith wafer processes that include similar environments (e.g., processingwith a fluorine environment).

As shown, the protective coating 215 (similar to coating 133, 134, and136 in FIG. 1 ) is formed on an article 210 or on multiple articles210A, 210B (such as any of the chamber components described before) byan accumulation of deposition materials 202 in the presence of energeticparticles 203 such as ions. The deposition materials 202 may includeatoms, ions, radicals, and so on. The energetic particles 203 mayimpinge and compact the protective coating 215 as it is formed.

In one embodiment, EB-IAD is utilized to form the protective coating215. FIG. 2B depicts a schematic of an IAD deposition apparatus. Asshown, a material source 250 provides a flux of deposition materials 202while an energetic particle source 255 provides a flux of the energeticparticles 203, both of which impinge upon the article 210, 210A, 210Bthroughout the IAD process. The energetic particle source 255 may beoxygen or other ion source. The energetic particle source 255 may alsoprovide other types of energetic particles such as radicals, neutrons,atoms, and nano-sized particles which come from particle generationsources (e.g., from plasma, reactive gases or from the material sourcethat provide the deposition materials).

The material source (e.g., a target body or a plug material) 250 used toprovide the deposition materials 202 may be a bulk sintered ceramiccorresponding to the same ceramic that the protective coating 215 is tobe composed of (e.g., a bulk sintered ceramic consisting of a singlephase of amorphous Y₂O₃—Al₂O₃). The material source may be a bulksintered ceramic compound body, such as bulk sintered YAG and bulksintered Al₂O₃, and/or other mentioned ceramics. Other target materialsmay also be used, such as powders, calcined powders, preformed material(e.g., formed by green body pressing or hot pressing), or a machinedbody (e.g., fused material). All of the different types of materialsources 250 are melted into molten material sources during deposition.However, different types of starting material take different amounts oftime to melt. Fused materials and/or machined bodies may melt thequickest. Preformed material melts slower than fused materials, calcinedpowders melt slower than preformed materials, and standard powders meltmore slowly than calcined powders.

In some embodiments, the material source is a metallic material (e.g., amixture of Y and Al, or two different targets, one of Y and one of Al).Such a material source may be bombarded by oxygen ions to form an oxidecoating. Additionally, or alternatively, an oxygen gas may be flowedinto a deposition chamber during the IAD process to cause the sputteredor evaporated metals of Y and Al to interact with oxygen and form anoxide coating.

IAD may utilize one or more plasmas or beams (e.g., electron beams) toprovide the material and energetic ion sources. Reactive species mayalso be provided during deposition of the plasma resistant coating. Inone embodiment, the energetic particles 203 include at least one ofnon-reactive species (e.g., Ar) or reactive species (e.g., O). Infurther embodiments, reactive species such as CO and halogens (Cl, F,Br, etc.) may also be introduced during the formation of a protectivecoating to further increase the tendency to selectively remove depositedmaterial most weakly bonded to the protective coating 215.

With IAD processes, the energetic particles 203 may be controlled by theenergetic ion (or other particle) source 255 independently of otherdeposition parameters. According to the energy (e.g., velocity), densityand incident angle of the energetic ion flux, composition, structure,crystalline orientation, grain size, and amorphous nature of theprotective coating may be manipulated.

Additional parameters that may be adjusted are a temperature of thearticle during deposition as well as the duration of the deposition. Inone embodiment, an IAD deposition chamber (and the chamber lid) isheated to a starting temperature of 70° C. or higher prior todeposition. In one embodiment, the starting temperature is 50° C. to250° C. In one embodiment, the starting temperature is 50° C. to 100° C.The temperature of the chamber and of the lid may then be maintained atthe starting temperature during deposition. In one embodiment, the IADchamber includes heat lamps which perform the heating. In an alternativeembodiment, the IAD chamber and lid are not heated. If the chamber isnot heated, it will naturally increase in temperature to about 70° C. asa result of the IAD process. A higher temperature during deposition mayincrease a density of the protective coating but may also increase amechanical stress of the protective coating. Active cooling can be addedto the chamber to maintain a low temperature during coating. The lowtemperature may be maintained at any temperature at or below 70° C. downto 0° C. in one embodiment.

Additional parameters that may be adjusted are working distance 270 andangle of incidence 272. The working distance 270 is the distance betweenthe material source 250 and the article 210A, 210B. In one embodiment,the working distance is 0.2 to 2.0 meters, with a working distance of1.0 meters in one particular embodiment. Decreasing the working distanceincreases a deposition rate and increases an effectiveness of the ionenergy. However, decreasing the working distance below a particularpoint may reduce a uniformity of the protective layer. The angle ofincidence is an angle at which the deposition materials 202 strike thearticles 210A, 210B. In one embodiment the angle of incidence is 10-90degrees.

IAD coatings can be applied over a wide range of surface conditions withroughness from about 0.1 micro-inches (pin) to about 180 μm. However,smoother surface facilitates uniform coating coverage. The coatingthickness can be up to about 300 microns (μm). In production, coatingthickness on components can be assessed by purposely adding a rare earthoxide based colored agent such Nd₂O₃, Sm₂O₃, Er₂O₃, etc. at the bottomof a coating layer stack. The thickness can also be accurately measuredusing ellipsometry.

IAD coatings can be amorphous or crystalline depending on the rare-earthoxide composite used to create the coating and/or the depositionconditions. Amorphous coatings are more conformal and reduce latticemismatch induced epitaxial cracks whereas crystalline coatings are moreerosion resistant. In one embodiments, the protective coating describedherein is amorphous and has zero crystallinity. In certain embodiments,the protective coating described herein is conformal and has a low filmstress.

Co-deposition of multiple targets using multiple electron beam (e-beam)guns can be achieved to create thicker coatings as well as layeredarchitectures. For example, two targets having the same material typemay be used at the same time. Each target may be bombarded by adifferent electron beam gun. This may increase a deposition rate and athickness of the protective layer. In another example, two targets maybe different ceramic materials. For example, one target of Al or Al₂O₃and another target of Y or Y₂O₃ may be used. A first electron beam gunmay bombard a first target to deposit a first protective layer, and asecond electron beam gun may subsequently bombard the second target toform a second protective layer having a different material compositionthan the first protective layer.

In an embodiment, a single target material (also referred to as plugmaterial) and a single electron beam gun may be used to arrive at theprotective coating described herein.

In one embodiment, multiple chamber components (e.g., multiple lids ormultiple liners) are processed in parallel in an IAD chamber. Eachchamber component may be supported by a different fixture.Alternatively, a single fixture may be configured to hold multiplechamber components. The fixtures may move the supported chambercomponents during deposition.

In one embodiment, a fixture to hold a chamber component can be designedout of metal components such as cold rolled steel or ceramics such asAl₂O₃, Y₂O₃, etc. The fixture may be used to support the chambercomponent above or below the material source and electron beam gun. Thefixture can have a chucking ability to chuck the chamber component forsafer and easier handling as well as during coating. Also, the fixturecan have a feature to orient or align the chamber component. In oneembodiment, the fixture can be repositioned and/or rotated about one ormore axes to change an orientation of the supported chamber component tothe source material. The fixture may also be repositioned to change aworking distance and/or angle of incidence before and/or duringdeposition. The fixture can have cooling or heating channels to controlthe chamber component's temperature during coating. The ability orreposition and rotate the chamber component may enable maximum coatingcoverage of 3D surfaces such as holes since IAD is a line of sightprocess.

FIG. 3 illustrates a cross sectional side view of an article that may becovered by one or more protective coatings (e.g., chamber componentssuch as lids and/or doors and/or liners and/or nozzles).

Referring to FIG. 3 , a body 305 of the chamber component 300 includes acoating stack 306 having a first protective coating 308 and a secondprotective coating 310. Alternatively, the article 300 may include onlya single protective coating 308 on the body 305. In one embodiment, theprotective coatings 308, 310 have a thickness of up to about 300 μm. Ina further embodiment, the protective coatings have a thickness of belowabout 20 microns, such as a thickness between about 0.5 microns to about12 microns, a thickness of between about 2 microns to about 12 microns,a thickness of about 5 microns to about 7 microns, or any sub-rangetherein or single thickness value therein. A total thickness of theprotective coating stack in one embodiment is 300 μm or less. In certainembodiments, the protective coating provides full coating coverage tothe underlying surface and is uniform in thickness. The uniformthickness of the coating across different sections of the coating may beevidenced by a variation in thickness that is about 15% or less, about10% or less, or about 5% or less in one section of the coating ascompared to another section of the coating.

The protective coatings 308, 310 are deposited ceramic layers that maybe formed on the body 305 of the article 300 using an electron beam ionassisted deposition (EB-IAD) process. The EB-IAD deposited protectivecoatings 308, 310 may have a relatively low film stress (e.g., ascompared to a film stress caused by plasma spraying or sputtering). Therelatively low film stress may cause the lower surface of the body 305to be very flat, with a curvature of less than about 50 microns over theentire body for a body with a 12 inch diameter.

The IAD deposited protective coatings 308, 310 has 0% porosity (i.e., noporosity) in embodiments. This low porosity may enable the chambercomponent to provide an effective vacuum seal during processing.Hermiticity measures the sealing capacity that can be achieved using theprotective coating. A He leak rate of around less than 1E-9 (cm³/s) canbe achieved using the IAD deposited protective coating, according to anembodiment. In comparison, a He leak rate of around 1E-6 cubiccentimeters per second (cm³/s) can be achieved using alumina. Lower Heleak rates indicate an improved seal. The hermiticity is measured byplacing a coated coupon over O-ring of Helium test stand and pumpingdown the pressure until the gauge <E-9 torr/s (or <1.3E-9 cm³/s),applying helium around the O-ring using a flow rate of helium of about30 sccm by slowly moving the helium source around the O-ring andmeasuring the leak rate.

The IAD deposited protective coating has a dense structure, which canhave performance benefits for application on a chamber lid for example.Additionally, the IAD deposited protective coating may have a low crackdensity and a high adhesion to the body 305, which can be beneficial forreducing cracks in the coating (both vertical and horizontal),delamination of the coating, yttrium-based particle generation by thecoating, and yttrium-based particle defects on a wafer.

In certain embodiments, the protective coatings described herein do notexhibit any gaps, pin holes or uncoated areas. In certain embodiments,the number of cracks (vertical or horizontal) in a protective coating donot exceed three in a 4 k magnification image obtained using a scanningelectron microscope (SEM) capable of resolution up to 20 k. In certainembodiments, there is no delamination of the coating and the adhesion ofthe coating is determined by measuring the amount of force used toseparate the protective coating from the substrate and is determined incompliance with ASTM standards (G171-03(2009) e2, C₁₆₂₄-05(2010),D7187-05). Adhesion strength of the protective coating to an aluminumsubstrate may be above 300 mN (milliNewton).

In certain embodiments, the roughness of the protective coating may beapproximately unchanged from the starting roughness of the underlyingsubstrate that is being coated. For instance, in certain embodiments,the starting roughness of the substrate may be about 8-16 micro-inchesand the roughness of the coating may be approximately unchanged. Incertain embodiments, the starting roughness of the underlying substratemay be lower than about 8 micro-inches, e.g. about 4 to about 8micro-inches, and the roughness of the protective coating may beapproximately unchanged. The protective coating may be polished toreduce a surface roughness to 8 micro-inches or below after deposition.The protective coating may be polished to reduce the surface roughnessto from about 4 micro-inches to about 8 micro-inches.

In certain embodiments, the protective coating has a high hardness thatmay resist wear during plasma processing. The IAD deposited protectivecoating, according to an embodiment, has a hardness of about ≥7 GPa,e.g., about 8.6 GPa. The hardness of the coating is determined bynano-indentation in accordance with ASTM E2546-07.

An IAD deposited protective coating, according to an embodiment, has abreakdown voltage of greater than 1823 V per 5 μm coating. The breakdownvoltage is determined in accordance with JIS C 2110.

The protective coatings described herein may have trace metals, such as,Ca (up to about 20 ppm), Cr (up to about 225 ppm), Cu (up to about 100ppm), Fe (up to about 1000 ppm), Mg (up to about 20 ppm), Mn (up toabout 20 ppm), Ni (up to about 200 ppm), K (up to about 20 ppm), Mo (upto about 2000 ppm), Na (up to about 40 ppm), Ti (up to about 50 ppm), Zn(up to about 20 ppm). Trace metal levels are determined using LaserAblation Inductively Coupled Plasma Mass Spectrometry (LA ICPMS) at adepth of 2 μm. In certain embodiments, the coating has a purity of about99.5% or more, about 99.6% or more, about 99.7% or more, about 99.8% ormore, or about 99.9% or more, based on atom % or based on wt % of theprotective coating.

Examples of other ceramics that may be used to form an adjacentprotective coating in an embodiment where the adjacent protectivecoatings 308, 310 are composed of different ceramic materials, mayinclude Y₃Al₅O₁₂, Y₄Al₂O₉, Er₂O₃, Gd₂O₃, Er₃Al₅O₁₂, Al₂O₃, Gd₃Al₅O₁₂, aceramic compound comprising Y₄Al₂O₉ and a solid-solution of Y₂O₃—ZrO₂(Y₂O₃—ZrO₂ solid solution), or any of the other ceramic materialspreviously identified.

Chamber components having IAD protective coatings may be used inapplications that apply a wide range of temperatures. For example,chamber components with IAD protective coatings may be used in processeshaving temperatures at 0° C. to temperatures at 1000° C. The coatedchamber components may be used at high temperatures (e.g., at or above300° C.) without cracking caused by thermal shock.

Note that the composition of the protective coating described herein maybe modified such that the material properties and characteristicsidentified above may vary by up to 30% in some embodiments. Accordingly,the described values for the protective coating properties should beunderstood as example achievable values. The protective coatingsdescribed herein should not be interpreted as being limited to theprovided values.

Any chamber component in a processing chamber may be coated with theprotective coating described herein, including but not limited to, alid, a lid liner, a nozzle, a substrate support assembly, a gasdistribution plate, a showerhead, an electrostatic chuck, a shadowframe, a substrate holding frame, a processing kit ring, a single ring,a chamber wall, a base, a liner kit, a shield, a plasma screen, a flowequalizer, a cooling base, a chamber viewport, or a chamber liner.

FIG. 4A illustrates a perspective view of a chamber lid 505 (similar tochamber lid 130 in FIG. 1 ) having a protective coating 510, inaccordance with one embodiment. FIG. 4B illustrates a cross-sectionalside view of a chamber lid 505 having a protective coating 510 (similarto coating 133 in FIG. 1 ), in accordance with one embodiment. Thechamber lid 505 includes a hole 520, which may be at a center of the lidor elsewhere on the lid. The lid 505 may also have a lip 515 that willbe in contact with walls of a chamber while the lid is closed. In oneembodiment, the protective coating 510 does not cover the lip 515. Toensure that the protective coating does not cover the lip 515, a hard orsoft mask may be used that covers the lip 515 during deposition. Themask may then be removed after deposition. Alternatively, the protectivelayer 510 may coat the entire surface of the lid. Accordingly, theprotective layer 510 may rest on side walls of a chamber duringprocessing.

As shown in FIG. 4B, the protective coating 510 may have a sidewallportion 530 that coats an interior of the hole 520. The sidewall portion530 of the protective layer 510 may be thicker near a surface of the lid505, and may gradually become thinner deeper into the hole 520. Thesidewall portion 530 may not coat an entirety of the sidewalls of thehole 520 in such embodiments.

FIG. 5 illustrates one embodiment of a method 500 for coating anarticle, such as a chamber component, with a protective coatingaccording to an embodiment. At block 505 of process 500, an article,such as a chamber component, is provided. The chamber component (e.g.,lid) may have a bulk sintered ceramic body. The bulk sintered ceramicbody may be Al₂O₃, Y₂O₃, SiO₂, or the ceramic compound comprisingY₄Al₂O₉ and a solid-solution of Y₂O₃—ZrO₂.

At block 510, an ion assisted deposition (IAD) process is performed todeposit a corrosion resistant and erosion resistant protective coatingonto at least one surface of the chamber component. In one embodiment,an electron beam ion assisted deposition process (EB-IAD) is performed.The IAD process may be performed by melting a material that is to bedeposited and bombarding the material with ions. While block 510describes performing ion assisted deposition, such as e-beam IAD, todeposit a corrosion and erosion resistant protective coating asdescribed herein, other deposition technique, such as physical vapordeposition and plasma spray deposition may also be utilized to depositprotective coatings described herein with a similar enhanced chemicalresistance to aggressive chemical environment and physical resistance toaggressive plasma environment. An exemplary physical vapor depositiontechnique is described with respect to FIG. 11 in further detail below.An exemplary plasma spray deposition technique is described with respectto FIG. 12 in further detail below.

The erosion resistant and corrosion resistant protective coating may bea single phase (e.g., amorphous) blend of yttrium oxide at a molarconcentration ranging from about 0.1 mole % to up to 37 mole % andaluminum oxide at a molar concentration ranging from above 63 mole % toabout 99.9 mole %. In certain embodiments, the protective coatingincludes yttrium oxide at a molar concentration ranging from about 10mole % to up to 37 mole % and aluminum oxide at a molar concentrationranging from above 63 mole % to about 90 mole %. In certain embodiments,the protective coating includes yttrium oxide at a molar concentrationranging from about 15 mole % to up to 37 mole % and aluminum oxide at amolar concentration ranging from above 63 mole % to about 85 mole %. Incertain embodiments, the protective coating includes yttrium oxide at amolar concentration ranging from about 5 mole % to about 35 mole % andaluminum oxide at a molar concentration ranging from about 65 mole % toabout 95 mole %. In certain embodiments, the protective coating includesyttrium oxide at a molar concentration ranging from about 5 mole % toabout 30 mole % and aluminum oxide at a molar concentration ranging fromabout 70 mole % to about 95 mole %. In certain embodiments, theprotective coating includes yttrium oxide at a molar concentrationranging from about 5 mole % to about 20 mole % and aluminum oxide at amolar concentration ranging from about 80 mole % to about 95 mole %.

A deposition rate for the protective coating may be about 0.02-20Angstroms per second (A/s) in one embodiment, and may be varied bytuning deposition parameters. In one embodiment, a deposition rate of0.25-1 A/s is initially used to achieve a conforming, well adheringcoating on the substrate. A deposition rate of 2-10 A/s may then be usedfor depositing a remainder of a protective coating to achieve a thickercoating in a shorter time. The protective coatings may be veryconforming, may be uniform in thickness, and may have a good adhesion tothe body/substrate that they are deposited on.

With IAD processes, the energetic particles may be controlled by theenergetic ion (or other particle) source independently of otherdeposition parameters. According to the energy (e.g., velocity), densityand incident angle of the energetic ion flux, composition, structure,and crystalline/amorphous nature of the protective coating may bemanipulated. Additional parameters that may be adjusted are atemperature of the article during deposition as well as the duration ofthe deposition.

The coating deposition rate can be controlled by adjusting an amount ofheat that is applied by an electron beam. The ion assist energy may beused to densify the coating and to accelerate the deposition of materialon the surface of the lid or nozzle. The ion assist energy can bemodified by adjusting the voltage and/or the current of the ion source.The current and voltage can be adjusted to achieve high and low coatingdensity, to manipulate the stress of the coating, and also to affect theamorphous nature of the coating. The ion assist energy can be used tomanipulate the structure (e.g., crystalline/amorphous nature) of theprotective coating and to change a stoichiometry of the protectivelayer. For example, a metallic target can be used, and during depositionmetallic material converts to a metal oxide by the incorporation ofoxygen ions at the surface of the lid or nozzle. Also, using an oxygengun the level of any metal oxide coating can be changed and optimized toachieve desired coating properties.

Coating temperature can be controlled by using heaters (e.g., heatlamps) and by controlling the deposition rate. A higher deposition ratewill typically cause the temperature of the chamber component toincrease. The deposition temperature can be varied to control a filmstress, crystallinity, and so on.

The working distance can be adjusted to modify uniformity, density anddeposition rate. The deposition angle can be varied by the location ofthe electron beam gun or electron beam hearth, or by changing a locationof the lid or nozzle in relation to the electron beam gun or electronbeam hearth. By optimizing the deposition angle, a uniform coating inthree dimensional geometries can be achieved.

FIG. 6 illustrates a method 600 for processing a wafer in a processingchamber that includes at least one chamber component coated with any ofthe protective coatings described herein. Method 600 includestransferring a wafer into a processing chamber that includes at leastone chamber component (e.g., a lid, a liner, a door, a nozzle, and soon) coated with a protective coating (615). Method 600 further includesprocessing the wafer in the processing chamber at a harsh chemicalenvironment and/or a high energy plasma environment (620). Theprocessing environment may include halogen-containing gases andhydrogen-containing gases, such as C₂F₆, SF₆, SiCl₄, HBr, NF₃, CF₄,CRF₃, CH₂F₃, F, NF₃, Cl₂, CCl₄, BCl₃, SiF₄, H₂, Cl₂, HCl, HE, amongothers, and other gases such as O₂, or N₂₀. In one embodiment, the wafermay be processed in Cl₂. In one embodiments, the wafer may be processedin H₂. In one embodiment, the wafer may be processed in HBr. Method 600further includes transferring the processed wafer out of the processingchamber (625).

Wafers processed according to methods described herein in processingchambers having at least one chamber component coated with a protectivecoating according to an embodiment exhibit a lower number ofyttrium-based particle defects thereon. For instance, wafers processedaccording to method described herein exhibit, on average, less thanabout 5, less than about 4, less than about 3, less than about 2, lessthan about 1, less than about 0.5, or less than about 0.1 yttrium-basedparticle defects per wafer. Protective coatings described hereinadvantageously reduce defectivity on processed wafers.

FIG. 8 depicts a schematic illustrating the number of yttrium-basedparticle defects on wafers processed over 700 radio frequency hours(RFhr) under harsh chemical conditions, including exposure to aggressiveCl₂, H₂, and fluorine based chemistry. As depicted in FIG. 8 , suchchemistry results in early chamber part failure with traditional YObased coating materials, shown by data series 810 (e.g., as early as 50RFhr). In comparison, with the protective coating composition describedherein (shown as data series 820), no elevated yttrium based particlesor yttrium based particle defects are observed and good performance ismaintained over extended duration of 700 RFhr.

FIG. 9 depicts the reduced number in yttrium-based defects observed fromchamber components coated with a protective coating according to anembodiment. As depicted in FIG. 9 , upon exposure to aggressivechemistry, traditional YO based coating materials, shown by data series830, result in yttrium-based particles ranging from above 5 up to about25. In comparison, with the protective coating composition describedherein (shown as data series 840), the number of yttrium based particlesis close to zero.

FIGS. 10A through 10D depicts the enhanced chemical resistance of theprotective coatings described herein as compared to other coatingsdeposited by the same deposition technique upon exposure of the variouscoatings to an acid stress test.

FIG. 10A depicts a YO coating deposited via e-beam IAD. As seen in FIG.10A, upon exposure of the YO coating to an acid stress test, the YOcoating exhibits heavy chemical damage.

FIG. 10B depicts a YAM coating deposited via e-beam IAD. As seen in FIG.10B, upon exposure of the YAM coating to an acid stress test, the YAMcoating exhibits heavy chemical damage.

FIG. 10C depicts a YAG coating deposited via e-beam IAD. As seen in FIG.10C, upon exposure of the YAG coating to an acid stress test, the YAGcoating exhibits mild chemical damage.

FIG. 10D depicts a coating according to embodiments described hereindeposited via e-beam IAD. As seen in FIG. 10D, upon exposure of acoating according to embodiments described herein to an acid stresstest, the coating exhibits no chemical damage.

Without being construed as limiting, it can be appreciated from FIGS.10A to 10D, that with increasing aluminum/alumina concentration in thecoating composition, the chemical resistance of the coating (asdetermined based on an acid stress test) improved.

As previously indicated, any of the protective coatings described hereinmay also be deposited by other techniques, such as PVD or plasma spray.These techniques are described in further detail below with respect toFIGS. 11 and 12 respectively.

PVD processes may be used to deposit thin films with thicknesses rangingfrom a few nanometers to several micrometers. The various PVD processesshare three fundamental features in common: (1) evaporating the materialfrom a solid source with the assistance of high temperature or gaseousplasma; (2) transporting the vaporized material in vacuum to thearticle's surface; and (3) condensing the vaporized material onto thearticle to generate a thin film layer. An illustrative PVD reactor isdepicted in FIG. 11 .

FIG. 11 depicts a deposition mechanism applicable to a variety of PVDtechniques and reactors. PVD reactor chamber 1100 may comprise a plate1110 adjacent to the article 1120 and a plate 1115 adjacent to thetarget 1130. In certain embodiments, a plurality of targets (e.g., twotargets) may be used. Air may be removed from reactor chamber 1100,creating a vacuum. Then gas (such as argon gas or oxygen gas) may beintroduced into the reactor chamber, voltage may be applied to theplates, and a plasma comprising electrons and positive ions (such asargon ions or oxygen ions) 1140 may be generated. Ions 1140 may bepositive ions and may be attracted to negatively charged plate 1115where they may hit one or more target(s) 1130 and release atoms 1135from the target. Released atoms 1135 may get transported and depositedas a coating 1125 onto article 1120. The coating may have a single layerarchitecture or may include a multi-layer architecture (e.g., layers1125 and 1145).

Article 1120 in FIG. 11 may represent various semiconductor processchamber components including but not limited to substrate supportassembly, an electrostatic chuck (ESC), a ring (e.g., a process kit ringor single ring), a chamber wall, a base, a gas distribution plate, gaslines, a showerhead, a nozzle, a lid, a liner, a liner kit, a shield, aplasma screen, a flow equalizer, a cooling base, a chamber viewport, achamber lid, and so on.

Coating 1125 (and optionally 1145) in FIG. 11 may represent any of theprotective coatings described herein. Coating 1125 (and optionally 1145)can have the same composition of aluminum/alumina, yttria/yttrium, andoxygen as the coatings previously described. Similarly, Coating 1125(and optionally 1145) can have any of the properties describedhereinbefore, such as, without limitations, percent amorphous, porosity,adhesion strength, chemical resistance, physical resistance, hardness,purity, breakdown voltage, hermeticity, and so on. Furthermore, coating1125 (and optionally 1145) can exhibit similar reduced defectivity (asestimated based on yttrium-based particle defects per wafer) uponexposure to aggressive chemical environment and/or to aggressive plasmaenvironment over extended duration (e.g., 700 RFhrs).

FIG. 12 depicts a sectional view of a plasma spray device 1200 accordingto an embodiment. The plasma spray device 1200 is a type of thermalspray system that is used to perform “slurry plasma spray” (“SPS”)deposition of ceramic materials. While the description below will bedescribed with respect to the SPS technique, other standard plasma spraytechniques may also be utilized to deposit the coatings describedherein.

SPS deposition utilizes a solution-based distribution of particles (aslurry) to deposit a ceramic coating on a substrate. The SPS may beperformed by spraying the slurry using atmospheric pressure plasma spray(APPS), high velocity oxy-fuel (HVOF), warm spraying, vacuum plasmaspraying (VPS), and low pressure plasma spraying (LPPS).

The plasma spray device 1200 may include a casing 1202 that encases anozzle anode 1206 and a cathode 1204. The casing 1202 permits gas flow1208 through the plasma spray device 1200 and between the nozzle anode1206 and the cathode 1204. An external power source may be used to applya voltage potential between the nozzle anode 1206 and the cathode 1204.The voltage potential produces an arc between the nozzle anode 1206 andthe cathode 1204 that ignites the gas flow 1208 to produce a plasma gas.The ignited plasma gas flow 1208 produces a high-velocity plasma plume1214 that is directed out of the nozzle anode 1206 and toward asubstrate 1220.

The plasma spray device 1200 may be located in a chamber or atmosphericbooth. In some embodiments, the gas flow 1208 may be a gas or gasmixture including, but not limited to argon, oxygen, nitrogen, hydrogen,helium, and combinations thereof. In certain embodiments, other gases,such as fluorine, may be introduced to incorporate some fluorine intothe coating so that it is more resistant to wear in a fluorineprocessing environment.

The plasma spray device 1200 may be equipped with one or more fluidlines 1212 to deliver a slurry into the plasma plume 1214. In someembodiments, several fluid lines 1212 may be arranged on one side orsymmetrically around the plasma plume 1214. In some embodiments, thefluid lines 1212 may be arranged in a perpendicular fashion to theplasma plume 1214 direction, as depicted in FIG. 12 . In otherembodiments, the fluid lines 1212 may be adjusted to deliver the slurryinto the plasma plume at a different angle (e.g., 45°), or may belocated at least partially inside of the casing 1202 to internallyinject the slurry into the plasma plume 1214. In some embodiments, eachfluid line 1212 may provide a different slurry, which may be utilized tovary a composition of a resulting coating across the substrate 1220.

A slurry feeder system may be utilized to deliver the slurry to thefluid lines 1212. In some embodiments, the slurry feeder system includesa flow controller that maintains a constant flow rate during coating.The fluid lines 1212 may be cleaned before and after the coating processusing, for example, de-ionized water. In some embodiments, a slurrycontainer, which contains the slurry fed to the plasma spray device1200, is mechanically agitated during the course of the coating processkeep the slurry uniform and prevent settling.

Alternatively, in standard powder based plasma spray techniques, apowder delivery system, that includes one or more powder containersfilled with one or more different powders, may be used to deliver powderinto the plasma plume 1214 (not shown).

The plasma plume 1214 can reach very high temperatures (e.g., betweenabout 3000° C. to about 10000° C.). The intense temperature experiencedby the slurry (or slurries) when injected into the plasma plume 1214 maycause the slurry solvent to evaporate quickly and may melt the ceramicparticles, generating a particle stream 1216 that is propelled towardthe substrate 1220. In a standard powder based plasma spray technique,the intense temperature of the plasma plume 1214 also melts the powderdelivered thereto and propels the molten particles toward the substrate1220. Upon impact with the substrate 1220, the molten particles mayflatten and rapidly solidify on the substrate, forming a ceramic coating1218. The solvent may be completely evaporated prior to the ceramicparticles reaching the substrate 1220.

Protective coatings deposited using plasma spray deposition may, incertain embodiments, have a greater porosity than that of coatingsdeposited by e-beam IAD. For instance, in certain embodiments, plasmaspray deposited protective coatings may have a porosity of up to about10%, up to about 8%, up to about 6%, up to about 4%, up to about 3%, upto about 2%, up to about 1%, or up to about 0.5%.

The parameters that can affect the thickness, density, and roughness ofthe ceramic coating include the slurry conditions, the particle sizedistribution, the slurry feed rate, the plasma gas composition, the gasflow rate, the energy input, the spray distance, and substrate cooling.

Article 1220 in FIG. 12 may represent various semiconductor processchamber components including but not limited to substrate supportassembly, an electrostatic chuck (ESC), a ring (e.g., a process kit ringor single ring), a chamber wall, a base, a gas distribution plate, gaslines, a showerhead, a nozzle, a lid, a liner, a liner kit, a shield, aplasma screen, a flow equalizer, a cooling base, a chamber viewport, achamber lid, and so on.

Coating 1218 in FIG. 12 may represent any of the protective coatingsdescribed herein. Coating 1218 can have the same composition ofaluminum/alumina, yttria/yttrium, and oxygen as the coatings previouslydescribed. Similarly, Coating 1218 can have any of the propertiesdescribed hereinbefore, such as, without limitations, percent amorphous,porosity, adhesion strength, chemical resistance, physical resistance,hardness, purity, breakdown voltage, hermeticity, and so on.Furthermore, Coating 1218 can exhibit similar reduced defectivity (asestimated based on yttrium-based particle defects per wafer) uponexposure to aggressive chemical environment and/or to aggressive plasmaenvironment over extended duration (e.g., 700 RFhrs).

The preceding description sets forth numerous specific details such asexamples of specific systems, components, methods, and so forth, inorder to provide a good understanding of several embodiments of thepresent invention. It will be apparent to one skilled in the art,however, that at least some embodiments of the present invention may bepracticed without these specific details. In other instances, well-knowncomponents or methods are not described in detail or are presented insimple block diagram format in order to avoid unnecessarily obscuringthe present invention. Thus, the specific details set forth are merelyexemplary. Particular implementations may vary from these exemplarydetails and still be contemplated to be within the scope of the presentinvention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearances of the phrase “in oneembodiment” or “in an embodiment” in various places throughout thisspecification are not necessarily all referring to the same embodiment.In addition, the term “or” is intended to mean an inclusive “or” ratherthan an exclusive “or.” When the term “about” or “approximately” is usedherein, this is intended to mean that the nominal value presented isprecise within ±30%.

Although the operations of the methods herein are shown and described ina particular order, the order of the operations of each method may bealtered so that certain operations may be performed in an inverse orderor so that certain operation may be performed, at least in part,concurrently with other operations. In another embodiment, instructionsor sub-operations of distinct operations may be in an intermittentand/or alternating manner.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Many other embodiments will beapparent to those of skill in the art upon reading and understanding theabove description. The scope of the invention should, therefore, bedetermined with reference to the appended claims, along with the fullscope of equivalents to which such claims are entitled.

1-6. (canceled)
 7. A method of coating a chamber component, comprising:performing electron beam ion assisted deposition (e-beam IAD), physicalvapor deposition (PVD), or plasma spray to deposit a protective coatingon a chamber component, wherein the protective coating comprises asingle phase blend of yttrium oxide at a molar concentration rangingfrom about 0.1 mole % up to 37 mole % and aluminum oxide at a molarconcentration ranging from above 63 mole % to about 99.9 mole %.
 8. Themethod of claim 7, wherein the protective coating is amorphous and has alow film stress.
 9. The method of claim 7, wherein the protectivecoating comprises yttrium oxide at a molar concentration ranging fromabout 10 mole % up to about 37 mole % and aluminum oxide at a molarconcentration ranging from above 63 mole % to about 90 mole %.
 10. Themethod of claim 7, wherein the protective coating comprises yttriumoxide at a molar concentration ranging from about 5 mole % to about 20mole % and aluminum oxide at a molar concentration ranging from about 80mole % to about 95 mole %.
 11. The method of claim 7, wherein thechamber component comprises a lid, a lid liner, a nozzle, a substratesupport assembly, a gas distribution plate, a showerhead, anelectrostatic chuck, a shadow frame, a substrate holding frame, aprocessing kit ring, a single ring, a chamber wall, a base, a liner kit,a shield, a plasma screen, a flow equalizer, a cooling base, a chamberviewport, or a chamber liner.
 12. The method of claim 7, wherein theprotective coating is chemically resistant to corrosive chemistry and isphysically resistant to high energy plasma, and wherein the corrosivechemistry comprises hydrogen-based chemistry, halogen-based chemistry,or a mixture thereof.
 13. A method of processing a wafer, comprising:processing a wafer in a chamber comprising at least one chambercomponent coated with a protective coating, wherein the protectivecoating comprises a single phase blend of yttrium oxide at a molarconcentration ranging from about 0.1 mole % to about 35 mole % andaluminum oxide at a molar concentration ranging from above 63 mole % toabout 99.9 mole %.
 14. The method of claim 13, wherein the processingoccurs at corrosive chemistry, high energy plasma, or combinationthereof.
 15. The method of claim 14, wherein the method exhibits, onaverage, less than about 1 yttrium-based particle defects per wafer. 16.The method of claim 13, wherein the protective coating comprises yttriumoxide at a molar concentration ranging from about 10 mole % up to 37mole % and aluminum oxide at a molar concentration ranging from above 63mole % to about 90 mole %.
 17. The method of claim 13, wherein theprotective coating comprises yttrium oxide at a molar concentrationranging from about 5 mole % to about 20 mole % and aluminum oxide at amolar concentration ranging from about 80 mole % to about 95 mole %. 18.The method of claim 13, wherein the at least one chamber componentcomprises a lid, a lid liner, a nozzle, a substrate support assembly, agas distribution plate, a showerhead, an electrostatic chuck, a shadowframe, a substrate holding frame, a processing kit ring, a single ring,a chamber wall, a base, a liner kit, a shield, a plasma screen, a flowequalizer, a cooling base, a chamber viewport, or a chamber liner. 19.The method of claim 13, wherein the protective coating is chemicallyresistant to corrosive chemistry and is physically resistant to highenergy plasma, and wherein the corrosive chemistry compriseshydrogen-based chemistry, halogen-based chemistry, or a mixture thereof.20. The method of claim 13, wherein the protective coating is amorphousand has a low film stress.